Polyetherimide esters exhibiting improved tensile elongation

ABSTRACT

Polyetherimide esters exhibiting improved tensile elongation comprised of the reaction products of (i) a diol mixture consisting essentially of butanediol and less than 70 mole percent of butenediol; (ii) at least one dicarboxylic acid or an ester forming reactive derivative thereof, and (iii) either at least one poly(oxy alkylene)diamine and at least one tricarboxylic acid or its derivative, or at least one polyoxyalkylene diimide diacid. 
     The instant polymers are suitable for extrusion and molding applications.

BACKGROUND OF THE INVENTION

Polyetherimide esters comprised of the reaction products of (a) a diol,(b) a dicarboxylic acid, (c) a poly(oxy alkylene)diamine, and (d) atricarboxylic acid or its derivative are known and are described in U.S.Pat. Nos. 4,544,734 and 4,556,705 to McCready and in U.S. Pat. No.4,556,688 to McCready et al. These polyetherimide esters exhibitexcellent stress-strain properties, low tensile set, high meltingtemperatures and/or excellent strength/toughness characteristics as wellas superior flexibility which are especially suitable for molding andextrusion applications.

It has now been discovered that by varying the diol reactantpolyetherimide esters can be provided which exhibit high or improvedtensile elongation. The polyetherimide esters exhibiting these hightensile elongation properties are obtained by utilizing as the diolreactant a mixture containing a butanediol and a butenediol.

SUMMARY OF THE INVENTION

In accordance with the instant invention there are providedpoly(etherimide ester) elastomers exhibiting high tensile elongationproperties. The polyetherimide esters of the instant invention arecomprised of the reaction products of (a) a diol mixture containing abutanediol and less than 70 mole percent of a butenediol, (b) at leastone dicarboxylic acid or an ester forming reactive derivative thereof,(c) at least one poly(oxy alkylene)diamine, and (d) at least onetricarboxylic acid having two vicinal carboxyl groups or derivativethereof.

DESCRIPTION OF THE INVENTION

In accordance with the instant invention there are providedpolyetherimide esters which exhibit high tensile elongation. Thepolyetherimide esters of the instant invention also exhibit high orimproved melt strength. The instant polymers, while exhibiting theseimproved properties, also exhibit the advantageous properties exhibitedby the polyetherimide esters generally.

The polyetherimide esters of the instant invention are comprised of thereaction products of:

(a) a diol component containing a mixture of butanediol and butenediol,the butenediol being present in said mixture in an amount less than 70mole percent;

(b) at least one dicarboxylic acid or its ester forming reactivederivative;

(c) at least one high molecular weight poly (oxy alkylene)diamine; and

(d) at least one tricarboxylic acid or a derivative thereof.

The diol component (a) contains a mixture of butenediol, preferably2-butene-1,4-diol, and butanediol, preferably 1,4-butanediol. The amountof butenediol present in this mixture is an amount effective to improvethe tensile elongation of the resultant polymer. This amount does notexceed, i.e., is less than, 70 mole percent, preferably less than about65 mole percent, and more preferably less than about 60 mole percent.The minimum amount of butenediol present is generally about 5 molepercent, preferably about 10 mole percent, and more preferably about 15mole percent. These amounts of butenediol are critical in providingpolymers exhibiting high tensile elongation. Outside theseconcentrations of butenediol there is no appreciable improvement intensile elongation over that exhibited by a polymer derived from 100mole % butanediol. Mole percent butenediol is calculated based on thetotal moles of butenediol and butanediol present in the diol mixture.

It is critical that the diol component contain this mixture ofbutenediol and butanediol in order to provide a polymer exhibitingimproved tensile elongation and melt strength. A polymer derived fromeither diol alone does not exhibit the increase in tensile elongation ofthe instant polymers.

The dicarboxylic acids (b) which are suitable for use in the practice ofthe present invention include the aliphatic, cycloaliphatic, and/oraromatic dicarboxylic acids. These acids are preferably of a lowmolecular weight, i.e., having a molecular weight of less than about300, however, higher molecular weight dicarboxylic acids, especiallydimer acids, may also be used. The term "dicarboxylic acids" as usedherein includes the equivalents of dicarboxylic acids having twofunctional carboxyl groups which perform substantially like dicarboxylicacids in reactions with glycols and diols in forming polyester polymers.These equivalents include, for example, esters and ester-formingreactive derivatives such as, for example, the acid halides, e.g.,diacid chlorides, and anhydrides. The molecular weight preferencementioned above pertains to the acid and not to its equivalent ester orester-forming reactive derivative. Thus, an ester of a dicarboxylic acidhaving a molecular weight greater than 300 or an acid equivalent of adicarboxylic acid having a molecular weight greater than 300 areincluded provided the acid has a molecular weight below about 300.Additionally, the dicarboxylic acids may contain any substituentgroup(s) or combinations which do not substantially interfere with thepolymer formation and the use of the polymer of this invention.

Aliphatic dicarboxylic acids, as the term is used herein, refers tocarboxylic acids having two carboxyl groups each of which is attached toa saturated carbon atom. If the carbon atom to which the carboxyl groupis attached is saturated and is in a ring, the acid is cycloaliphatic.

Aromatic dicarboxylic aclds, as the term is used herein, aredicarboxylic acids having two carboxyl groups each of which is attachedto a ring carbon atom in an isolated or fused benzene ring system. It isnot necessary that both functional carboxyl groups be attached to thesame aromatic ring and where more than one ring is present, they can bejoined by aliphatic or aromatic divalent radicals or divalent radicalssuch as --O-- or --SO₂ --.

Representative aliphatic and cycloaliphatic acids which can be used forthis invention include, for example, sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, glutaric acid, succinic acid, oxalicacid, azelaic acid, diethylmalonic acid, allylmalonic acid, dimer acid,4-cyclohexene-1,2-dicarboxylic acid, 2-ethylsuberic acid,tetramethylsuccinic acid, cyclopentanedicarboxylic acid,decahydro-1,5-naphthylene dicarboxylic acid, 4,4'-bicyclohexyldicarboxylic acid, decahydro-2,6-naphthalene dicarboxylic acid,4,4-methylenebis(cyclohexane carboxylic acid), 3,4-furan dicarboxylicacid, and 1,1-cyclobutanedicarboxylic acid. Preferred aliphatic acidsare cyclohexane dicarboxylic acids, sebacic acid, dimer acid, glutaricacid, azelaic acid and adipic acid.

Representative aromatic dicarboxylic acids which can be used includeterephthalic, phthalic and isophthalic acids, bi-benzoic acid,substituted dicarboxy compounds with two benzene nuclei such asbis(p-carboxyphenyl)methane, oxybis(benzoic acid),ethylene-1,2-bis(p-oxybenzoic acid), 1,5-naphthalene dicarboxylic acid,2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid,phenanthrene dicarboxylic acid, anthracene dicarboxylic acid,4,4'-sulfonyl dibenzoic acid, and halo and C₁ -C₁₂ alkyl, alkoxy, andaryl ring substitution derivatives thereof. Hydroxy acids such asp(betahydroxyethoxy)benzoic acid can also be used provided an aromaticdicarboxylic acid is also present.

Preferred dicarboxylic acids for the preparation of the polyetherimideesters of the present invention are the aromatic dicarboxylic acids,mixtures thereof and mixtures of one or more dicarboxylic acid with analiphatic and/or cycloaliphatic dicarboxylic acid, most preferably thearomatic dicarboxylic acids. Among the aromatic acids, those with 6-16carbon atoms are preferred, particularly the benzene dicarboxylic acids,i.e., phthalic, terephthalic and isophthalic acids and their dimethylderivatives. Especially preferred is dimethyl terephthalate.

Finally, where mixtures of dicarboxylic acids are employed in thepractice of the present invention, it is preferred that at least about60 mole %, preferably at least about 80 mole %, based on 100 mole % ofdicarboxylic acid (b) be of the same dicarboxylic acid or esterderivative thereof. As mentioned above, the preferred compositions arethose in which dimethylterephthalate is the predominant dicarboxylicacid, most preferably when dimethylterephthalate is the onlydicarboxylic acid.

The polyoxyalkylene diamines (c) suitable for use in the presentinvention may be characterized by the following general formula:

    H.sub.2 N--G--NH.sub.2                                     I.

wherein G is the radical remaining after the removal of the amino groupsof a long chain alkylene ether diamine. These polyether diprimarydiamines are available commercially from Texaco Chemical Company underthe trademark Jeffamine. In general they are prepared by known processesfor the amination of glycols. For example, they may be prepared byaminating the glycol in the presence of ammonia, Raney nickel catalystand hydrogen as set forth In Belgium Pat. No. 634,741. Alternately, theymay be prepared by treating the glycol with ammonia and hydrogen over aNickel-Copper-Chromium catalyst as taught by U.S. Pat. No 3,654,370.Other methods for the production thereof include those taught in U.S.Pat. Nos. 3,155,728 and 3,236,895 and French Pat. Nos. 1,551,605 and1,466,708, all of which are incorporated by reference.

The long chain ether diamines suitable for use herein are polymericdiamines having terminal (or as nearly terminal as possible) aminegroups and an average molecular weight of from about 600 to about12,000, preferably from about 900 to about 4,000. Additionally, the longchain ether diamines will generally have a carbon-to-oxygen ratio offrom about 1.8 to about 4.3.

Representative long chain ether diamines are the poly(alkyleneether)diamines including poly (ethylene ether)diamine, poly(propyleneether) diamine, poly(tetramethylene ether)diamine random or blockcopolymers of ethylene oxide and propylene oxide including propyleneoxide and poly(propylene oxide) terminated poly(ethylene ether)diamine;and aminated random or block copolymers of tetrahydrofuran with minoramounts of a second monomer such as ethylene oxide, propylene oxide, andmethyl tetrahydrofuran (used in proportions such that thecarbon-to-oxygen mole ratio in the diamine does not exceed about 4.3 to1). Polyformyl diamines prepared by reacting formaldehyde with diolssuch as 1,4-butanediol and 1,5-pentanediol and subsequent amination areuseful. Especially preferred poly(alkylene ether)diamines arepoly(propylene ether)diamine, poly(tetramethylene ether) diamine andpoly(ethylene ether)glycols end-capped with poly(propylene ether)glycoland/or propylene oxide and subsequently aminated.

In general, the polyoxyalkylene daimines usefl within the scope of thepresent invention will have an average molecular weight of from about600 to about 12,000, preferably from about 900 to about 4,000.

The tricarboxylic acid (d) may be almost any carboxylic acid anhydridecontaining an additional carboxylic group or the corresponding acidthereof containing two imide-forming vicinal carboxyl groups in lieu ofthe anhydride group. Mixtures thereof are also suitable. The additionalcarboxylic group must be esterifiable.

While trimellitic anhydride is preferred as the tricarboxylic acidcomponent, any number of suitable tricarboxylic acid constituents willoccur to those skilled in the art including 2,6,7-naphthalenetricarboxylic anhydride, 3,3',4-diphenyl tricarboxylic anhydride,3,3',4-benzophenone tricarboxylic anhydride, 1,3,4,-cyclopentanetricarboxylic anhydride, 2,2',3-diphenyl tricarboxylic anhydride,diphenyl sulfone-3,3',4-tricarboxylic anhydride, ethylene tricarboxylicanhydride, 1,2,5-naphthalene tricarboxylic anhydride, 1,2,4-butanetricarboxylic anhydride, 3,4-dicarboxyphenyl-3-carboxyphenyl etheranhydride, 1,3,4-cyclohexane tricarboxylic anhydride, and the like.These tricarboxylic acid materials may be characterized by the followinggeneral formula ##STR1## wherein:

R is a trivalent organic radical, preferably a trivalent C₂ -C₂₀alipahtic or cycloaliphatic or C₆ -C₂₀ aromatic radical. Preferredtrivalent radicals are the hydrocarbon radicals;

R' is preferably hydrogen or a monovalent organic radical preferablyselected from C₁ -C₆ aliphatic and/or cycloaliphatic radicals and C₆-C₁₂ aromatic radicals, e.g., benzyl, most preferably hydrogen.

The amount by which each of the foregoing reactants is employed in thepreparation of the polymers of the present invention is not, in general,critical and depends, in part, upon the desired properties of theresultant polymer. Obviously, sufficient amounts of diol versus diacidand tricarboxylic acid versus diamine must be present, as recognized inthe art, to allow for substantially complete polymerization.

This type of one-pot reaction involving the reactions of (a) a diol, (b)a dicarboxylic acid, (c) a poly(oxy alkylene)diamine, and (d) atricarboxylic acid is described in U.S. Pat. No. 4,556,588 to McCreadyet al, incorporated by reference. In this type of one-pot reaction toproduce the polyetherimide ester elastomer the amount of diol (a)employed will be, in general, a molar excess, preferably about 1.5 molarequivalents, based on the combined molar equivalents of dicarboxylicacid (b) and of the total moles of tricarboxylic acid (d). The amount oftricarboxylic acid (d) employed will preferably be about two molarequivalents based on the number of moles of the poly(oxyalkylene)diamine (c). Obviously, less than two molar equivalents wouldresult incomplete imidization of the diamine resulting in potentiallypoorer properties. Conversely, greater than two molar equivalents of thetricarboxylic acid (d) may lead to cross-linking and/or branching of thepolymer. Generally, mole ratios of 2 moles of tricarboxylic acid (d) to0.85 to 1.15 mole of poly(oxy alkylene)diamine have been found to yielduseful polymers. Finally, the amount by which the dicarboxylic acid (b)and the diamine (c) are used will be such that the weight ratio of thetheoretical amount of polyoxyalkylene diimide diacid formable from thediamine (c) and tricarboxylic acid (d) to the dicarboxylic acid (b) willbe from about 0.25 to about 2.0, preferably from about 0.4 to about 1.4.

The instant polyetherimide esters may also be prepared by a two-potreaction involving the reactions of (a) a diol component, (b) adicarboxylic acid, and (e) a polyoxyalkylene diimide diacid. Such atwo-pot reaction is described in U.S. Pat. No. 4,556,705 to McCready,incorporated herein by reference. Basically, in this process thepoly(oxy alkylene)diamine (c) is reacted with a tricarboxylic acid (d)to form a polyoxyalkylene diimide diacid (e), and said polyoxyalkylenediimide diacid is then reacted with the diol (a) and the dicarboxylicacid (b).

The polyoxyalkylene diimide diacid (e) may be represented by the generalformula ##STR2## wherein G, R and R' are as defined hereinafore.

The polyoxyalkylene diimide diiacids of Formula III suitable for useherein are high molecular weight diimide diacids wherein the averagemolecular weight is greater than about 700, most preferably greater thanabout 900. They may be prepared by the imidization reaction of one ormore tricarboxylic acid components (d) containing two vicinal carboxylgroups or an anhydride group and an additional carboxyl group which mustbe esterifiable and preferably is nonimidizable with a high molecularweight poly(oxy alkylene)diamine (c). These polyoxyalkylene diimidediacids and processes for their preparation are disclosed in said U.S.Pat. No. 4,556,705, to McCready, incorporated herein by reference.Briefly, these polyalkylene diimide diacids may be prepared by knownimidization reactions including melt synthesis or by synthesizing in asolvent system. Such reactions will generally occur at temperatures offrom 100° C. to 300° C., preferably at from about 150° C. to about 250°C. while drawing off water or in a solvent system at the refluxtemperature of the solvent or azeotropic (solvent) mixture.

In this two-pot process the weight ratio of the above ingredients, as inthe one-pot process, is also not critical. However, it is preferred thatthe diol be present in at least a molar equivalent amount, preferably amolar excess, most preferably at least 150 mole % based on the moles ofdicarboxylic acid (b) and polyoxyalkylene diimide diacid (e) combined.Such molar excess of diol will allow for optimal yields, based on theamount of acids, while accounting for the loss of diol duringesterification/condensation.

Further, while the weight ratio of the dicarboxylic acid (b) topolyoxyalkylene diimide diacid (e) is not critical preferredcompositions are those in which the weight ratio of the polyoxyalkylenediimide diacid (e) to dicarboxylic acid (b) is from about 0.25 to about2, preferably from about 0.4 to about 1.4. The actual weight ratio willbe dependent upon the specific polyoxyalkylene diimide diacid used andmore importantly upon the desired physical and chemical properties ofthe resultant polyetherimide ester.

It is likewise possible, as described in U.S. Pat. No. 4,556,688, toprepolymerize the aromatic dicarboxylic acid (b) and the diol (a) toform a prepolyester. Forming the prepolyester of (a) and (b) can beachieved by conventional esterification techniques as described in U.S.Pat. Nos. 2,465,319, 3,047,439 and 2,910,466, all of which areincorporated herein by reference.

In its preferred embodiments, the compositions of the instant inventioncomprise the reaction products of dimethylterephthalate, optionally withup to 40 mole percent of another dicarboxylic acid; a mixture ofbutanediol, preferably 1,4-butanediol, and butenediol, preferably2-butene-1,4-diol; and either (i) a poly(oxy alkylene) diamine of amolecular weight of from about 600 to about 12,000, preferably fromabout 900 to about 4,000, and trimellitic anhydride, or (ii) apolyoxyalkylene diimide diacid prepared from a poly(oxy alkylene)diamineof molecular weight of from about 600 to about 12,000, preferably fromabout 900 to about 4,000, and trimellitic anhydride. In its morepreferred embodiment the diol mixture will contain from about 05 tobelow 70 mole percent butenediol and the dicarboxylic acid will be 100mole percent dimethylterephthalate.

The instant polyetherimide esters may be prepared by conventionalesterification/condensation reactions for the production of polyesters.These processes are described, inter alia, in U.S. Pat. Nos. 3,763,109,3,651,014 and 3,801,547, all of which are incorporated herein byreference, and in U.S. Pat. Nos. 4,556,705 and 4,556,688, alsoincorporated herein by reference.

The polyetherimide esters of the instant invention contain at least thefollowing two general recurring structural units: ##STR3## wherein:

A is the residue of the polyoxyalkylene diimide diacid absent the twocarboxyl groups, e.g., ##STR4##

R¹ is the residue of the diol absent the two hydroxyl groups; and

R² is the residue of the dicarboxylic acid absent the two carboxylgroups.

Since, in the practice of the instant invention, the diol used is amixture of butanediol and butenediol IV and V will, in general, becomprised of two sub-formulae, i.e., one wherein R¹ is the residue ofbutanediol and one wherein R¹ is the residue of butenediol. Thus, thepolyetherimide esters of the instant invention generally contain atleast the following four recurring structural units: ##STR5## wherein:

A and R² are as defined hereinafore;

R^(1') is the residue of the butanediol absent the two hydroxyl groups,e.g., butylene radical; and

R^(1") is the residue of the butenediol absent the two hydroxyl groups,e.g., butenylene radical.

Since, in the instant invention, the amount of butenediol present in thediol mixture is from about 5 to below 70 mole percent, and since theamounts of units of Formulae IVb and Vb are generally related to anddependent upon the amount of butenediol present in the reaction mixture,the combined or total amounts of units IVb and Vb (IVb+Vb) present isfrom about 5 to below 70 mole percent. Conversely, since the amount ofthe butanediol present in the diol mixture is from above 30 to about 95mole percent, and since the amounts of recurring structural units IVaand Va (IVa+Va) present is generally related to and dependent upon theamount of butanediol present in the reaction mixture, the instantpolyetherimide ester will generally contain from above 30 to about 95mole percent of units IVa and Va. Amounts of units IVb and Vb presentare calculated based on the total amounts, in moles, of units IVa, IVb,Va and Vb present.

It is to be understood that under certain circumstances, particularlywhen utilizing processes other than the one-pot process describedhereinafore, polyetherimide esters of the instant invention can beproduced which are comprised of less than all four of the recurringstructural units IVa-Vb, but in no case containing less than tworecurring structural units of either Formulae lVa and Vb or Formulae IVband Va. Thus, for example, if a polyalkylene etherdiimide ester, i.e.,IV, is first prepolymerized separately (by the reaction of the diol,poly(oxy alkylene)diamine, and the tricarboxylic acid, or by thereaction of the diimide diacid and the diol) utilizing only one diol ofthe diol mixture, e.g. butenediol, and the polyester, i.e., V, is thenpolymerized utilizing the diol mixture of butenediol and butanediol,then the polyetherimide ester of the instant invention will comprise thethree recurring structural units IVb, Va and Vb. Conversely, if thepolyester, i.e., V, is first prepolymerized separately (by the reacttionof the dicarboxylic acid with the diol) using only one diol of the diolmixture, e.g., butenediol, and the polyalkylene etherdiimide ester,i.e., IV, is then polymerized utilizing the diol mixture of butanedioland butenediol, then the polyetherimide ester polymer of the instantinvention will contain the three recurring structural units IVa, IVb andVb.

In the process of the present invention for the preparation of thepolyetherimide ester polymers, particularly where all the reactants arecharged to the reactor together or where the polyoxyalkylene diimidediacid is preformed and excess tricarboxylic acid is present, a minoramount of the tricarboxylic acid or anhydride may react with theavailable hydroxyl groups and ultimately function as a branching agentin the finished polymer. Within limits, the degree of branching in thefinished polymer can be controlled by varying the mole ratio oftricarboxylic acid (d) to polyoxyalkylene diamine (c). An excess ofdiamine reduces the degree of branching, while an excess of thetricarboxylic acid increases branching. In addition to controllingbranching by varying the tricarboxylic acid/diamine mole ratio, one cancompensate for branching by introducing a monofunctional reactant suchas benzoic acid in minor amounts.

With reference to branching it should be noted that polymers of thisinvnetion, when prepared from preformed diimide-diacids, aresubstantially free of branching. If branching is desired, one needs onlyto introduce a branching agent such as trimellitic anhydride alomg withthe preformed diimidediacid The amount of branching agent generally willbe less than 0.15 mole per mole of diimidediacid or ester thereof.Useful branching agents other than trimellitic anhydride include, butare not limited to, trimethyl trimellitate, glycerol, trimethylolpropane, trimesic acid and its esters, and the like.

Additionally, while not required, it is customary and preferred toutilize a catalyst or catalyst system in the process for the productionof the polyether imide esters of the present invention. In general, anyof the known ester-interchange and polycondensation catalysts may beused. Although two separate catalysts or catalyst systems may be used,one for ester interchange and one for polycondensation, it is preferred,where appropriate, to use one catalyst or catalyst system for both. Inthose instances where two separate catalysts are used, it is preferredand advantageous to render the ester-interchange catalyst ineffectivefollowing the completion of the precondensation reaction by means ofknown catalyst inhibitors or quenchers, in particular, phosphoruscompounds such as phosphoric acid, phosphenic acid, phosphonic acid andthe alkyl or aryl esters or salts thereof, in order to increase thethermal stability of the polymer.

Exemplary of the suitable known catalysts there may be given theacetates, carboxylates, hydroxides, oxides, alcoholates or organiccomplex compounds of zinc, manganese, antimony, cobalt, lead, calciumand the alkali metals insofar as these compounds are soluble in thereaction mixture. Specific examples include zinc acetate, calciumacetate and combinations thereof with antimony tri-oxide and the like.These catalysts, as well as additional useful catalysts are described inU.S. Pat. Nos. 2,465,319, 2,534,028, 2,850,483, 2,892,815, 2,937,160,2,998,412, 3,047,549, 3,110,693 and 3,385,830, among other, incorporatedherein by reference.

Where the reactants and reactions allow it is preferred to use thetitanium catalysts including the inorganic and organic titaniumcontaining catalysts, such as those described, for example, in U.S. Pat.Nos. 2,720,502, 2,727,881, 2,729,619, 2,822,348, 2,906,737, 3,047,515,3,056,817, 3,056,818 and 3,075,952, all of which are incorporated hereinby reference. Especially preferred are the organic titanates such astetra-butyl titanate, tetra-isopropyl titanate, and tetra-octyl titanateand the complex titanates derived from alkali or alkaline earth metalalkoxides and titanate esters, most preferably organic titanates. Thesetoo may be used alone or in combination with other catalysts such as forexample, zinc acetate, calcium acetate, magnesium acetate or antimonytrioxide, and/or with a catalyst quencher as described. The catalystshould be used in catalytic amounts, i.e., from about 0.005 to about 2.0percent by weight based on total reactants.

Both batch and continous methods can be used for any stage of the etherimide ester polymer preparation. Polycondensation of the polyesterprepolymer with the poly(oxy alkylene) diimide diacid can also beaccomplished in the solid phase by heating finely divided solidpolyester prepolymer with the diimide diacid in a vacuum or in a streamof inert gas to remove liberated low molecular weight diol. This methodhas the advantage of reducing degradation because it must be used attemperatures below the softening point of the prepolymer. The majordisadvantage is the long time required to reach a given degree ofpolymerization.

Although the copolyetherimide esters of this invention possess goodresistance toward heat aging and photodegradation, it is advisable tostabilize these compounds by the addition of a antioxidant.

Many of the oxidative and/or thermal stabilizers known in the art forcopolyesters may be used in the practice of the present invention. Thesemay be incorporated into the composition either during polymerization orwhile in a hot melt stage following polymerization. Satisfactorystabilizers include the phenols and their derivatives, amines and theirderivatives, compounds containing both hydroxyl and amine groups,hydroxyazines, oximes, polymeric phenolic esters and salts ofmultivalent metals in which the metal is in its lower valence state.Some specific examples of these stabilizers are described in U.S. Pat.No. 4,556,688, incorporated herein by reference.

The instant compositions can be stabilized against ultraviolet radiationby the addition thereto of the well known ultraviolet radiationabsorbers such as, for example, the substituted benzophenones andbenzotriazoles.

Further, the properties of these polymers can be modified byincorporation of various conventional and well known inorganic fillerssuch as carbon black, silica gel, alumina, clays, and choppedfiberglass. These may be incorporated in amounts up to 50% by weight,preferably up to about 30% by weight.

The polymers of the instant invention may also optionally contain thevarious well known flame retardants such as, for example, the halogenand/or sulfur containing organic and inorganic compounds.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The following examples are presented to more fully illustrate thepresent invention. They are presented as illustrative of the presentinvention and are not to be construed as limiting thereof. In theexamples all parts and percentages are parts and percentages by weightunless otherwise specified.

The following examples illustrate compositions falling outside the scopeof the instant invention. They are presented for comparative purposesonly.

EXAMPLE 1

This examples illustrates a polyetherimide ester derived from 100 molepercent 1,4-butanediol as the diol reactant.

To a reactor vessel there are charged 4767 parts by weight of1,4-butanediol, 4320 parts by weight of polyoxyalkylene diimide diacid(prepared by the imidization of trimellitic anhydride with TexacoChemical Company's Jeffamine® D2000, a polypropylene ether diamineaverage molecular weight 2,000), 6129 parts by weight of dimethylterephthalate, a phenolic stabilizer, and a titanate catalyst. Thereactor is heated at 160° C. whereupon methanol was generated. Themethanol is distilled and the temperature is gradually raised to 240° C.After heating at this temperature for over an hour vacuum is applied andthe polymer is removed.

The following properties of the polymer are determined, and the resultsare set forth in Table I:

melt viscosity (MV) in poise determined in accordance with modified testmethod ASTM D1238;

% tensile elongation determined in accordance with test method ASTMD638;

flexural modulus, psi×10³, in accordance with test method ASTM D790;

tensile strength, at break and at yield, in accordance with test methodASTM D790; and

flexural strength in accordance with test method ASTM D790.

EXAMPLE 2

This example illustrates a polyetherimide ester derived from a diolcomponent containing 100 mole percent butenediol.

The procedure of Example 1 is substantially repeated except that intothe reactor are charged 209 parts by weight of butenediol, 189 parts byweight of polyoxyalkylene diimide diacid of the type used in Example 1,and 270 parts by weight of dimethyl terephthalate.

The properties of the resultant polymer are determined and the resultsare set forth in Table I.

EXAMPLE 3

This example illustrates a polyetherimide ester derived from a diolcomponent containing 90 mole percent butenediol and 10 mole percentbutanediol.

The procedure of Example 2 is substantially repeated except into thereactor are charged 188 parts by weight of butenediol and 21 parts byweight of butanediol.

The properties of the resultant polymer are determined and the resultsare set forth in Table I.

EXAMPLE 4

This example illustrates a polyetherimide ester derived from a diolcomponent containing 70 mole percent butenediol and 30 mole percentbutanediol.

The procedure of Example 2 is substantially repeated except that intothe reactor are charged 146 parts by weight of butenediol and 63 partsby weight of butanediol.

The properties of the resultant polymer are determined and the resultsare set forth in Table I.

The following examples illustrate compositions falling within the scopeof the instant invention.

EXAMPLE 5

This example illustrates a polyetherimide ester derived from a diolcomponent containing 25 mole percent butenediol and 75 mole percentbutanediol.

The procedure of Example 2 is substantially repeated except that intothe reactor are charged 50 parts by weight of butenediol and 150 partsby weight of butanediol.

The properties of the resultant polymer are determined and the resultsare set forth in Table I.

EXAMPLE 6

This example illustrates a polyetherimide ester derived from a diolcomponent containing 50 mole percent butenediol and 50 mole percentbutanediol.

The procedure of Example 2 is substantially repeated except into thereactor are charged 105 parts by weight of butenediol and 105 parts byweight of butanediol.

The properties of the resultant polymer are determined and the resultsare set forth in Table I.

EXAMPLE 7

This example illustrates a polyetherimide ester derived from a diolcomponent containing 50 mole percent butenediol and 50 mole percentbutanediol. However, in contradistinction to the compositions ofExamples 1-6 where the mole ratio of dimethyl terephthalate topolyoxyalkylene diimide diacid was the same, the amount of dimethylterephthalate is increased relative to that of the polyoxyalkylenediimide diacid over that used in Examples 1-6.

The procedure of Example 1 is substantially repeated except that intothe reactor vessel are charged 126 parts by weight of butenediol, 126parts by weight of butanediol, 324 parts by weight if dimethylterephthalate, and 113 parts by weight of polyoxyalkylene diimide diacidof the type used in Example 1.

The properties of the resultant polymer are determined and the resultsare set forth in Table I.

                                      TABLE I                                     __________________________________________________________________________                                           tensile                                Example                                                                            mole %                                                                              mole % melt % tensile                                                                           flexural                                                                           flexural                                                                           strength                               No.  butenediol*                                                                         butanediol**                                                                         viscosity                                                                          elongation                                                                          modulus                                                                            strength                                                                           at yield                                                                          at break                           __________________________________________________________________________    1     0    100    2900 160   24,000                                                                             1500 2400                                                                              3200                               2    100    0     3870  90   29,000                                                                             1700 2200                                                                              2200                               3    90    10     --    95   19,000                                                                             1300 2000                                                                              2400                               4    70    30     --   160   14,000                                                                              700 1500                                                                              2200                               5    25    75     1350 270   23,000                                                                             1350 1800                                                                              2900                               6    50    50     2150 240   19,000                                                                             1090 1500                                                                              2700                               7    50    50     --   260   41,000                                                                             2500 2600                                                                              3200                               __________________________________________________________________________     *2-butene-1,4-diol                                                            **1,4butanediol                                                          

As illustrated by the data in Table I the polymers of the instantinvention (Examples 5-7) exhibit higher or better tensile elongationthan polymers derived from either 100 mole percent butanediol or 100mole percent butenediol, Examples 1 and 2 respectively. That theaddition of butenediol to butanediol would be effective in improving thetensile elongation of a polymer derived from such a diol mixture issurprising and unexpected since a polymer derived from butenediol has alower tensile elongation value than a polymer derived from butanediol.Yet the polymers of the instant invention exhibit higher tensileelongation than polymers derived from 100 mole % butanediol.

Likewise, polymers derived from a mixture of butenediol and butanediolhave lower melt viscosities than a polymer derived from butanediol.Since a polymer derived from butenediol has a higher melt viscosity thana polymer derived from butanediol it is indeed unexpected and surprisingthat adding a butenediol to butanediol would yield a polymer having alower melt viscosity than a polymer derived from butanediol alone.

That not just any ratio of butanediol to butenediol is effective inimproving the tensile elongation of polyetherimide esters is illustratedby the data of Examples 3 and 4. In order to obtain a polymer having atensile elongation greater than that of a polymer derived from 100 mole% butanediol it is necessary that the amount of butenediol present inthe diol mixture is below 70 mole %.

Example 7 illustrates that the improvement in tensile elongation of thepolyetherimide esters is exhibited by polyetherimide esters derived fromwide ratios of dicarboxylic acid to polyoxyalkylene diimide diacid.

Obviously other modifications and variations of the present inventionare possible in light of the above teachings. It is, therefor, to beunderstood that changes may be made in the particular embodiments of theinvention described which are within the full intended scope as definedby the appended claims.

What is claimed is:
 1. A polyetherimide ester composition comprising thereaction products of:(i) a mixture of butanediol and butenediol whereinthe amount of butenediol present in said mixture is less than 70 molepercent; (ii) at least one dicarboxylic acid or an ester formingreactive derivative thereof; and (iii) a set of reactants selectedfrom(a) (i) at least one high molecular weight poly(oxyalkylene)diamine, and (ii) at least one tricarboxylic acid or aderivative thereof, or (b) at least one polyoxyalkylene diimide diacid.2. The composition of claim 1 wherein said diol mixture contains lessthan about 65 mole percent of butenediol.
 3. The composition of claim 2wherein said diol mixture contains less than about 60 mole percent ofbutenediol.
 4. The composition of claim 1 wherein said butenediol is2-butene-1,4-diol.
 5. The composition of claim 1 wherein said butanediolis 1,4-butanediol.
 6. The composition of claim 1 wherein saiddicarboxylic acid (ii) is selected from C₂ -C₁₆ alipahtic orcycloaliphatic dicarboxylic acids, C₆ to C₁₆ aromatic dicarboxylicacids, ester equivalents of said aliphatic, cycloaliphatic, or aromaticacids, or mixtures thereof.
 7. The composition of claim 6 wherein saiddicarboxylic acid (ii) is from about 60 to 100 mole percent dimethylterephthalate.
 8. The composition of claim 7 wherein said dicarboxylicacid (ii) is from about 80 to about 100 mole percent dimethylterephthalate.
 9. The composition of claim 8 whereins said dicarboxylicacid (ii) is 100 mole percent dimethyl terephthalate.
 10. Thecomposition of claim 1 wherein (iii) is at least one high molecularweight poly(oxy alkylene diamine), and at least one tricarboxylic acidor derivative thereof.
 11. The composition of claim 10 wherein saidpoly(oxy alkylene)diamine is represented by the formula

    H.sub.2 N--G--NH.sub.2

wherein G is the radical remaining after the removal of amino groups ofa long chain alkylene ether diamine and the poly(oxy alkylene)diaminehas an average molecular weight of from about 600 to about 12,000. 12.The composition of claim 11 wherein the average molecular weight of saidpoly(oxy alkylene) diamine is from about 900 to about 4,000.
 13. Thecomposition of claim 11 wherein the poly(oxyalkylene)diamine is derivedfrom a long chain ether glycol selected from poly(ethylene ether)glycol,poly(propylene ether)glycol, poly(tetramethylene ether) glycol,copoly(propylene ether-ethylene ether)glycol, or mixtures thereof. 14.The composition of claim 13 wherein said long chain ether glycol ispoly(propylene ether) glycol.
 15. The composition of claim 10 whereinsaid tricarboxylic acid is represented by the formula ##STR6## wherein Ris a C₂ to C₂₀ trivalent aliphatic or cycloaliphatic radical, or atrivalent C₆ to C₂₀ aromatic radical, and R' is hydrogen or a C₁ to C₆aliphatic radical.
 16. The composition of claim 15 wherein saidtricarboxylic acid is trimellitic anhydride.
 17. The composition ofclaim 10 wherein the weight ratio of the theoretical amount ofpolyoxyalkylene diimide diacid formable from the diamine (iii)(a)(i) andtricarboxylic acid (iii)(a)(ii) to the amount of dicarboxylic acid (ii)is from about 0.25 to about 2.0.
 18. The composition of claim 17 whereinsaid weight ratio of said polyoxyalkylene diimide diacid to saiddicarboxylic acid is from about 0.4 to about 1.4.
 19. The composition ofclaim 1 wherein (iii) is at least one polyxoyalkylene diimide diacid(b).
 20. The composition of claim 19 wherein said polyoxyalkylenediimide diacid is derived from at least one poly(oxy alkylene)diamineand at least one tricarboxylic acid containing two vicinal carboxylgroups or an anhydride groups and an additional carboxyl group.
 21. Thecomposition of claim 20 wherein said polyoxyalkylene diimide diacid isrepresented by the formula ##STR7## wherein each R is independentlyselected from C₂ to C₂₀ aliphatic or cycloaliphatic trivalent organicradicals, or C₆ to C₂₀ aromatic trivalent organic radicals; each R' isindependently selected from hydrogen, C₁ to C₆ aliphatic orcycloaliphatic monovalent organic radicals, or C₆ -C₁₂ aromaticmonovalent organic radicals; and G is the divalent radical remainingafter removal of the two amino groups of a long chain ether diaminehaving an average molecular weight of from about 600 to about 12,000.22. The composition of claim 21 wherein the polyoxyalkylene diimidediacid is such that each R is a C₆ trivalent aromatic hydrocarbonradical, each R' is hydrogen, and G is the radical remaining afterremoval of the amino groups of a long chain ether diamine having anaverage molecular weight of from about 900 to about 4,000.
 23. Thecomposition of claim 21 wherein said polyoxyalkylene diimide diacid isderived from trimellitic anhydride and a poly(oxy alkylene)diamineselected from poly(oxy propylene)diamine and a copoly(ethyleneoxide-propylene oxide)diamine having predominately polethylene oxide inthe backbone.
 24. The composition of claim 19 wherein the weight ratioof said polyoxyalkylene diimide diacid to said dicarboxylic acid (ii) isfrom about 0.25 to about 2.0
 25. The composition of claim 24 whereinsaid weight ration of said polyoxyalkylene diimide diacid to saiddicarboxylic acid (ii) is from about 0.4 to about 1.4.
 26. Apolyetherimide ester polymer comprised of at least the following tworecurring strutural units: ##STR8## wherein: R¹ is independentlyselected from a mixture of the residues of butanediol and butenediolabsent the two hydroxyl groups, said mixture containing less than 70mole percent of the residue of butenediol;A is the residue of a highmolecular weight polyoxyalkylene diimide diacid absent the two carboxylgroups; and R² is the residue of a dicarboxylic acid absent the twocarboxyl groups.
 27. The polymer of claim 26 wherein A is represented bythe formula ##STR9## wherein: each R is independently selected fromtrivalent organic radicals selected from C₂ -C₂₀ aliphatic orcycloaliphatic or C₆ -C₂₀ aromatic trivalent organic radicals; andG isthe divalent radical remaining after removal of the amino groups of along chain poly(oxy alkylene) diamine having an average molecular weightof from about 600 to about 12,000.
 28. The polymer of claim 26 whereinR² is the divalent residue of a C₂ -C₁₆ aliphatic or cycloaliphaticdicarboxylic acid or a C₆ -C₁₆ aromatic dicarboxylic acid.
 29. Thepolymer of claim 28 wherein R² is the residue of an aromaticdicarboxylic acid.
 30. The polymer of claim 27 wherein said polymer iscomprised of at least the following recurring structural units:##STR10## wherein: R^(1') is the residue of butanediol absent the twohydroxyl groups, andR^(1") is the residue of butenediol absent the twohydroxyl groups,said polymer containing a combined amount of recurringstructural units (b) and (d) which is less than 70 mole percent, basedon the total amounts of units (a), (b), (c) and (d) present.
 31. Thepolymer of claim 30 wherein R² is the divalent residue absent the twocarboxylic groups of a C₂ -C₁₆ alipahtic or cycloaliphatic or C₆ -C₁₆aromatic dicarboxylic acid.
 32. The polymer of claim 30 wherein G is thedivalent radical remaining after removal of the amino groups of a longchain poly(oxy alkylene)diamine having an average molecular weight offrom about 900 to about 4,000.
 33. The polymer of claim 32 wherein saidR² is the residue of dimethyl terephthalate.
 34. The polymer of claim 30wherein the combined amount of units (b) and (d) is less than about 65mole percent.
 35. The polymer of claim 34 wherein the combined amount ofunits (b) and (d) is less than about 60 mole percent.